Monomer, polymer, and ocular lens comprising the same

ABSTRACT

Monomers for polymers having high oxygen permeability, high water content and a low modulus of elasticity are provided, and polymers and ophthalmic lenses comprised of said monomers are provided. They are monomers represented by formula (1) or (2) below: 
     X—O—(CH 2 CH 2 CH 2 O) m —(CH 2 ) n—A    ( 1 ) 
     
       
         
         
             
             
         
       
     
     wherein, X is a polymerizable group having carbon-carbon unsaturated bonds; A is a siloxanyl group; R is H or a methyl group; m is an integer of 1 to 10; m′ is an integer of 2 to 10; and n is an integer of 2 to 10.

TECHNICAL FIELD

[0001] This invention relates to monomers, polymers and ophthalmiclenses in which they are used. This invention is particularly suited touse in ophthalmic lenses such as contact lenses, intraocular lenses andartificial corneas.

PRIOR ART

[0002] In recent years, 3-methacryloxypropyltris (trimethylsiloxy)silane has been widely used for polymers having high oxygenpermeability, and, particular, as a monomer for ophthalmic lenses(Japanese Patent Application Laid-Open No. 60[1985]-142324 and JapanesePatent Application Laid-Open No. 54[1979]-24047). However, because3-methacryloxypropyltris (trimethylsiloxy) silane has essentially nohydrophilic properties, polymers that are obtained from it have a lowwater content. This is not desirable for ophthalmic lenses. Further,polymers that are obtained from 3-methacryloxypropyltris(trimethylsiloxy) silane have a comparatively high modulus of elasticityso that it is difficult to use them for soft contact lenses.

[0003] A monomer represented by formula (10) below is described in, forexample, Japanese Patent Application Laid-Open No. 60[1985]-131518.

[0004] When the monomer of formula (10) is used, there is a tendency forpolymers having higher water content and a lower modulus of elasticityto be obtained than when 3-methacryloxypropyltris (trimethylsiloxy)silane is used. However, this modulus of elasticity is not sufficientand a lower modulus of elasticity is still needed.

DISCLOSURE OF THE INVENTION

[0005] This invention has the objective of solving the aforementionedproblems and of providing monomers for polymers having high oxygenpermeability and also high water content and a low modulus ofelasticity. It has the further objective of providing polymers comprisedof said monomers, and ophthalmic lenses.

[0006] In order to achieve the aforementioned objectives, the monomersand polymers of this invention have the structure indicated below.

[0007] [1] A monomer that is represented by formula (1) or (2) below:

X—O—(CH₂CH₂CH₂O)_(m)—(CH₂)n—A  (1)

[0008]

[0009] wherein, X is a polymerizable group having carbon-carbonunsaturated bonds; A is a siloxanyl group; R is H or a methyl group; mis an integer of 1 to 10; m′ is an integer of 2 to 10; and n is aninteger of 2 to 10.

[0010] [2] A polymer comprising the monomer of [1] above as apolymerization component.

EMBODIMENT OF THE INVENTION

[0011] We shall now describe the embodiment of this invention. Themonomers of this invention are characterized in that they arerepresented by formula (1) or (2) below:

X—O—(CH₂CH₂CH₂0_(m)—(CH₂)_(n)—A  (1)

[0012]

[0013] wherein, X is a polymerizable group having carbon-carbonunsaturated bonds; A is a siloxanyl group; R is H or a methyl group; mis an integer of 1 to 10; m′ is an integer of 2 to 10; and n is aninteger of 2 to 10.

[0014] In this formula, X is a polymerizable group having carbon-carbonunsaturated bonds. Specific examples can include the groups representedby formulas (4) to (9) below. Of these, the groups represented byformulas (4) and (5) are preferable from the standpoints of ease ofsynthesis and level of polymerization characteristics, and the grouprepresented by formula (5) is the most desirable:

[0015] wherein, in formulas (4) through (9), R¹ is H or a methyl group.

[0016] In formula (1) or (2), A is a siloxanyl group. The term siloxanylgroup in this specification indicates a group that has at least oneSi—O—Si bond. Substituents as represented by formula (3) below aredesirable for use as siloxanyl groups:

[0017] wherein, in formula (3), A¹ to A¹¹, respectively andindependently, are H, alkyl groups of 1 to 20 carbon atoms that may besubstituted or aryl groups of 6 to 20 carbon atoms that may besubstituted; k is an integer of 0 to 200;

[0018] and a, b and c, respectively and independently, are integers of 0to 20, excepting the case k=a=b=c=0.

[0019] In formula (3), A¹ to A¹¹, respectively and independently, are H,alkyl groups of 1 to 20 carbon atoms that may be substituted or arylgroups of 6 to 20 carbon atoms that may be substituted. Specificexamples can include H, alkyl groups such as methyl groups, ethylgroups, propyl groups, isopropyl groups, butyl groups, isobutyl groups,sec-butyl groups, t-butyl groups, hexyl groups, cyclohexyl groups,2-ethylhexyl groups and octyl groups and aryl groups such as phenylgroups and naphthyl groups. Of these, methyl groups are the mostdesirable.

[0020] In formula (3), k is an integer of 0 to 200, preferably, of 0 to50, and, more preferably, of 0 to 10. a, b and c are, respectively andindependently, integers of 0 to 20, and, preferably, independently andrespectively, integers of 0 to 5. When k=0, the combinations of a, b andc should be a=b=c=1, a=b=1 and c=0, and a=1 and b =C=0.

[0021] Of the substituents represented by formula (3), those that areparticularly desirable because they can be acquired comparativelycheaply on an industrial basis are tris (trimethylsiloxy) siylyl groups,methylbis (trimethylsiloxy) silyl groups, dimethyl (trimethylsiloxy)silyl groups, polydimethylsiloxane groups, polymethylsiloxane groups andpoly-co-methylsiloxane-dimethylsiloxane groups.

[0022] In formula (1), m is an integer of 1 to 10. However, from thestandpoint of balance of the oxygen permeability with high water contentand low modulus of elasticity of the polymers obtained from saidmonomers, m should be 1 or 2, and, most preferably, 1.

[0023] Further, in formula (2), m′ is an integer of 2 to 10. However,from the standpoint of balance of the oxygen permeability with highwater content and low modulus of elasticity of the polymers obtainedfrom said monomers, m′ should be 2 or 3, and, most preferably, 2.

[0024] In formulas (1) and (2), n is an integer of 2 to 10. From thestandpoint of ease of synthesis, n should be 2 or 3, and, mostpreferably, 3.

[0025] The following method can be presented as an example of the methodof synthesis of the monomers represented by formula (1). First, acompound represented by formula (11):

H—O—(CH₂CH₂CH₂O)_(m)—H  (11)

[0026] wherein, in formula (11), m is an integer of 1 to 10 and R is Hor a methyl group,

[0027] is reacted with a compound represented by formula (12):

Z—(CH₂)_(n−2)—CH═CH₂  (12)

[0028] wherein, in formula (12), Z is elimination groups such as I, Br,Cl and p-toluenesulfonyloxy groups and n is an integer of 2 to 10,

[0029] in the presence of a base such as potassium hydroxide or sodiumhydride, to obtain a compound as represented by formula (13):

H—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n−2)—CH═CH₂  (13)

[0030] wherein, in formula (13), m is an integer of 1 to 10, n is aninteger of 2 to 10, and R is H or a methyl group.

[0031] Then, by reacting the compound represented by formula (13) with asuitable compound having carbon-carbon unsaturated bonds, a compoundrepresented by formula (14)

X—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n−2)—CH═CH₂  (14)

[0032] is obtained. The suitable compound having carbon-carbonunsaturated bonds differs depending on the type of X. For example, whenX is a group represented by formula (4), it is the corresponding epoxycompound, when X are groups represented by formula (5), formula (8) andformula (9), it is the corresponding halide and when X are groupsrepresented by formula (6) and formula (7), it is the correspondingisocyanate compound. Next, a compound as represented by formula (14) isreacted with a compound as represented by formula (15)

[0033] in the presence of a hydrosilylated catalyst of which platinumsystems are represented, with a monomer as represented by formula (1)being obtained. At this time, a chlorosilane compound can be usedinstead of the compound represented by formula (15). When a chlorosilanecompound is used, the monomer represented by formula (1) can be obtainedby condensing the chlorosilane addition product that is obtained with analkoxysilane compound or a chlorosilane compound in the presence ofwater.

[0034] Further, the following method can be presented as an example ofthe synthesis of monomers represented by formula (2). First, a compoundrepresented by formula (16):

[0035] wherein, in formula (16), R is H or a methyl group and m′ is aninteger or 2 to 10,

[0036] is reacted with a compound represented by the aforementionedformula (12), in the presence of a base such as potassium hydroxide orsodium hydride, and a compound represented by formula (17) is obtained:

[0037] wherein, in formula (17), R is H or a methyl group, m′ is aninteger of 2 to 10, and n is an integer of 2 to 10.

[0038] Next, the compound represented by formula (17) is reacted with asuitable compound having carbon-carbon unsaturated bonds, by which meansa compound represented by formula (18) is obtained.

[0039] The suitable compound having carbon-carbon unsaturated bondsdiffers depending on the type of X. For example, when X is a grouprepresented by formula (4), it is the corresponding epoxy compound, whenX are groups represented by formula (5), formula (8) and formula (9), itis the corresponding halide and when X are groups represented by formula(6) and formula (7), it is the corresponding isocyanate compound. Next,the compound represented by formula (18) is reacted with the compoundrepresented by the aforementioned formula (15) in the presence of ahydrosilylated catalyst of which platinum systems are representatives,and a monomer as represented by formula (2) is obtained. At this time, achlorosilane compound can be used instead of the compound represented byformula (15). When a chlorosilane compound is used, the monomerrepresented by formula (2) can be obtained by condensing thechlorosilane addition product that is obtained with an alkoxysilanecompound or a chlorosilane compound in the presence of water.

[0040] The polymers of this invention can be obtained by polymerizingthe monomers represented by formulas (1) or (2) individually or they canbe obtained by copolymerization with other monomers. In the case ofcopolymerization with other monomers, there are no particularlimitations on the copolymerization monomers as long as they can becopolymerized, and monomers having (meth)acryloyl groups, styryl groups,allyl groups, vinyl groups and other copolymerizable carbon-carbonunsaturated bonds can be used.

[0041] We shall now present several examples of suitable other monomers.However, they are not limited to these examples. They can include(meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, vinylbenzoic acid; alkyl (meth)acrylates such as methyl (meth)acrylate andethyl (meth)acrylate; polyfunctional (meth)acrylates such aspolyalkylene glycol mono(meth)acrylate, polyalkylene glycolmonoalkylether (meth)acrylate, polyalkylene glycol bis(meth)acrylate,trimethylolpropanetris (meth)acrylate, pentaerythritoltetrakis(meth)acrylate and siloxane macromers having carbon-carbon unsaturatedbonds in both terminals; halogenated alkyl (meth)acrylates such astrifluoroethyl (meth)acrylate and hexafluoroisopropyl (meth)acrylate;hydroxyalkyl (meth)acrylates having hydroxy groups such as2-hydroxyethyl (meth)acrylate and 2,3-dihydroxypropyl (meth)acrylate;(meth)acrylamides such as N,N-dimethyl acrylamide, N,N-diethylacrylamide, N,N-di-n-propyl acrylamide, N,N-diisopropyl acrylamide,N,N-di-n-butyl acrylamide, N-acryloyl morpholine, N-acryloyl piperidine,N-acryloyl pyrrolidine and N-methyl (meth)acrylamide; aromatic vinylmonomers such as styrene, a-methylstyrene and vinyl pyridine;maleimides; heterocyclic vinyl monomers such as N-vinyl pyrrolidone,N-vinyl caprolactam, N-vinyl oxasolidone, 1-vinyl imidazole, N-vinylcarbazole, vinyl pyridine and vinyl pyrazine; N-vinyl carboxamides suchas N-vinyl formamide, N-vinyl acetamide and N-methyl-N-vinyl acetamide;vinyl esters such as vinyl acetate; 3-[tris(trimethylsiloxy)silyl]propyl (meth)acrylate, 3-[bis(trimethylsiloxy)methylsilyl] propyl(meth)acrylate, 3-[(trimethylsiloxy)dimethylsilyl] propyl(meth)acrylate, 3-[tris(trimethylsiloxy)silyl] propyl (meth)acrylamide,3-[bis(trimethylsiloxy)methylsilyl] propyl (meth)acrylamide,3-[(trimethylsiloxy)dimethylsilyl] propyl (meth)acrylamide,[tris(trimethylsiloxy)silyl] methyl (meth)acrylate,[bis(trimethylsiloxy)methylsilyl] methyl (meth)acrylate,[(trimethylsiloxy)dimethylsilyl] methyl (meth)acrylate,[tris(trimethylsiloxy)silyl] methyl (meth)acrylamide,[bis(trimethylsiloxy)methylsilyl] methyl (meth)acrylamide,[(trimethylsiloxy)dimethylsilyl] methyl (meth)acrylamide,[tris(trimethylsiloxy)silyl] styrene, [bis(trimethylsiloxy)methylsilyl]styrene, [(trimethylsiloxy)dimethylsilyl] styrene,N-[3-[tris(trimethylsiloxy)silyl]propyl] vinyl carbamide,N-[3-[bis(trimethylsiloxy)methylsilyl]propyl] vinyl carbamide,N-[3-[(trimethylsiloxy)dimethylsilyl]propyl] vinyl carbamide andcompounds of formulas (19) to (21) indicated below:

[0042] wherein, in formulas (19) to (21), R¹¹ is H or a methyl group ands is an integer of 1 to 3.

[0043] For the purpose of obtaining good mechanical properties and ofobtaining good resistance to disinfecting solutions and washingsolutions, in the polymer of this invention, it is desirable to usemonomers having two or more copolymerizable carbon-carbon unsaturatedbonds in one molecule as copolymerization components. Thecopolymerization ratio of monomers having two or more copolymerizablecarbon-carbon unsaturated bonds in one molecule should be 0.1 weight %to 70 weight %, and, preferably, 0.2 weight % to 40 weight %.

[0044] From the standpoint of achieving both high oxygen permeabilityand high water content, it is desirable to copolymerize and use monomersrepresented by formula (1) or (2) for the polymers of this invention. Inthis case, the copolymerization ratio of monomers represented by formula(1) or (2) should be 30 weight % to 97 weight %, preferably, 50 weight %to 95 weight %, and, more preferably, 60 weight % to 90 weight %. Whenthe copolymerization ratio of the monomers represented by formula (1) or(2) is too low, oxygen permeability of the polymer is decreased. When itis too high, there is a tendency for water content to decrease.

[0045] The polymers of this invention may also contain ultravioletabsorbents, pigments and colorants. Ultraviolet absorbents, pigments andcolorants having polymerizable groups may also be present incopolymerized form.

[0046] When the polymers of this invention are obtained by(co)polymerization, thermal polymerization initiators andphotopolymerization initiators, of which peroxides and azo compounds arerepresentative, may be added to facilitate polymerization. When thermalpolymerization is performed, substances having optimum dissolutionproperties at the desired reaction temperature are selected and used. Ingeneral, azo initiators and peroxide initiators having 10 hourshalf-life temperatures of 40 to 120° C. are desirable. Carbonylcompounds, peroxides, azo compounds, sulfur compounds, halides and metalsalts can be cited as photopolymerization initiators. Thesepolymerization initiators can be used individually or in mixtures andare used in quantities up to about 1 weight %.

[0047] Polymerization solvents can be used when the polymers of thisinvention are obtained by (co)polymerization. Various organic andinorganic solvents can be used as solvents and there are no particularlimitations on them. Examples that can be cited include water, alcoholsolvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol,isopropyl alcohol, normal butyl alcohol, isobutyl alcohol and tert-butylalcohol; glycol ether solvents such as methyl cellosolve, ethylcellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycolmonomethyl ether, ethylene glycol dimethyl ether, diethylene glycoldimethyl ether and triethylene glycol dimethyl ether; ester solventssuch as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate andmethyl benzoate; aliphatic hydrocarbon solvents such as normal hexane,normal heptane and normal octane; alicyclic hydrocarbon solvents such ascyclohexane and ethyl cyclohexane; ketone solvents such as acetone,methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbonsolvents such as benzene, toluene and xylene; and petroleum solvents.They can be used individually or in mixtures.

[0048] Known polymerization methods and molding methods can be used forthe polymers of this invention. For example, there is a method in whichthey are polymerized and molded into rods or plates and are processed tothe desired shapes by cutting and processing, a mold polymerizationmethod and a spin cast polymerization method.

[0049] As an example, we shall now describe the case in which thepolymers of this invention are obtained by the mold polymerizationmethod.

[0050] A monomer composition is filled into the space of two moldshaving a fixed shape. Photopolymerization or thermal polymerization isperformed and it is formed to the shape of the mold. The mold can bemade of resin, glass, ceramics or metal. In the case ofphotopolymerization, a material that is optically transparent is used,and, ordinarily, resin or glass is used. In many cases, when the polymeris manufactured, a space is formed by the two opposing molds and thespace is filled with the monomer composition. Depending on the shape ofthe mold and the properties of the monomer, a gasket may be used for thepurpose of conferring a fixed thickness on the polymer and of preventingleakage of the filled monomer composition. The mold into the space ofwhich the monomer composition is filled, is then irradiated with activelight rays such as ultraviolet rays or is introduced into an oven orwater bath or oil bath to heat and polymerize. The two methods can alsobe used in combination, with thermal polymerization being performedafter photopolymerization, or, conversely, photopolymerization can beperformed after thermal polymerization. In the case ofphotopolymerization, for example, light containing a large portion ofultraviolet rays is usually irradiated for a short time (ordinarily 1hour or less) using a mercury lamp or an insect attraction lamp as thelight source. When thermal polymerization is performed, the temperatureis gradually raised from close to room temperature, being increased to atemperature of 60° C. to 200° C. over a period of several hours toseveral tens of hours. These conditions are desirable for the purpose ofmaintaining the optical homogeneity and quality of the polymer and ofincreasing reproducibility.

[0051] The polymers of this invention can be subjected to modificationtreatments by various methods. It is desirable to perform saidmodification treatments for the purpose of increasing surfacewettability.

[0052] Specific modification methods of polymers can includeelectromagnetic waves (including light) irradiation, plasma irradiation,chemical vapor deposition treatments such as vaporization andsputtering, heating, treatment with bases, treatment with acids and theuse of other suitable surface treatment agents, and combinations ofthese treatments. Of these modification procedures, treatment with basesand treatment with acids are desirable because they are simple.

[0053] Examples of treatments with bases or treatments with acids thatcan be cited include a method in which the polymer is brought intocontact with a basic or acidic solution and a method in which thepolymer is brought into contact with a basic or acidic gas. Morespecific examples of these methods include, for example, methods inwhich the polymer is immersed in a basic or acidic solution, methods inwhich a basic or acidic solution or basic or acidic gas is sprayed atthe polymer, methods in which the basic or acidic solution is applied tothe polymer with a spatula or brush and methods in which the basic oracidic solution is applied to the polymer by a spin coating method or adip coating method. The method whereby great modifying effects can beobtained most simply is the method in which the polymer is immersed inthe basic or acidic solution.

[0054] There are no particular limitations on temperature when thepolymer is immersed in the basic or acidic solution. However, theprocedure is usually performed in a temperature range of approximately−50° C. to 300° C. When workability is considered, a temperature rangeof −10° C. to 150° C. is preferable and −5° C. to 60° C. is morepreferable.

[0055] The optimum period for immersion of the polymer in the basic oracidic solution varies depending on the temperature. In general, aperiod of up to 100 hours is desirable, a period of up to 24 hours ismore preferable and a period of up to 12 hours is most preferable. Whencontact time is too long, workability and productivity deteriorate andthere are instances in which there are such deleterious effects asdecrease of oxygen permeability and decrease of mechanical properties.

[0056] The bases that can be used include alkali metal hydroxides,alkaline earth metal hydroxides, various carbonates, various borates,various phosphates, ammonia, various ammonium salts, various amines andhigh molecular weight bases such as polyethylene imines and polyvinylamines. Of these, alkali metal hydroxides are the most desirable becausethey are inexpensive and very effective.

[0057] The acids that can be used include various inorganic acids suchas sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid,various organic acids such as acetic acid, formic acid, benzoic acid andphenol and high molecular weight acids such as polyacrylic acids,polymethacrylic acids, polystyrene sulfonic acids and polysulfomethylstyrene. Of these, high molecular weight acids are the most desirablebecause of their great treatment effectiveness and little deleteriouseffect on other physical properties.

[0058] Various inorganic and organic solvents can be used as solvents ofthe basic or acidic solution. For example, they can include water;various alcohols such as methanol, ethanol, propanol, 2-propanol,butanol, ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, polyethylene glycol and glycerol; various aromatichydrocarbons such as benzene, toluene and xylene; various aliphatichydrocarbons such as hexane, heptane, octane, decane, petroleum ether,kerosene, ligroin and paraffin; various ketones such as acetone, methylethyl ketone and methyl isobutyl ketone; various esters such as ethylacetate, butyl acetate, methyl benzoate and dioctyl phthalate; variousethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycoldialkyl ether, diethylene glycol dialkyl ether, triethylene glycoldialkyl ether, tetraethylene glycol dialkyl ether and polyethyleneglycol dialkyl ether; various nonprotonic polar solvents such asdimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone,dimethylimidazolidinone, hexamethyl phosphoric triamide and dimethylsulfoxide; halogen solvents such as methylene chloride, chloroform,dichloroethane trichloroethane and trichloroethylene; and freonsolvents. Of these, water is the most desirable from the standpoints ofeconomic factors, convenience of handling and chemical stability. Thesesolvents can also be used in mixtures of two or more.

[0059] The basic or acidic solutions that are used in this invention mayalso contain components other than the basic substances or acidicsubstances and the solvents.

[0060] In this invention, after the polymer has been subjected totreatment with a base or an acid, the basic or acidic substance can beremoved by washing.

[0061] Various inorganic and organic solvents can be used as washingsolvents. For example, they can include water; various alcohols such asmethanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol,polyethylene glycol and glycerol; various aromatic hydrocarbons such asbenzene, toluene and xylene; various aliphatic hydrocarbons such ashexane, heptane, octane, decane, petroleum ether, kerosene, ligroin andparaffin; various ketones such as acetone, methyl ethyl ketone andmethyl isobutyl ketone; various esters such as ethyl acetate, butylacetate, methyl benzoate and dioctyl phthalate; various ethers such asdiethyl ether, tetrahydrofuran, dioxane, ethylene glycol dialkyl ether,diethylene glycol dialkyl ether, triethylene glycol dialkyl ether,tetraethylene glycol dialkyl ether and polyethylene glycol dialkylether; various nonprotonic polar solvents such as dimethylformamide,dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone,hexamethyl phosphoric triamide and dimethyl sulfoxide; halogen solventssuch as methylene chloride, chloroform, dichloroethane trichloroethaneand trichloroethylene; and freon solvents. Generally, water is the mostdesirable.

[0062] Mixtures of two or more of these solvents can be used as thewashing solvent. The washing solvent may also contain components otherthan the solvents, for example, inorganic salts, surfactants anddetergents.

[0063] The entire polymer may be subjected to said modificationtreatment or it may be performed on only a portion of the polymer, forexample, the surface. When only the surface is subjected to modificationtreatment, wettability of the surface can be improved without makinggreat changes in the polymer as a whole.

[0064] The oxygen permeability coefficient of the polymer of thisinvention should be greater than 50×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)],preferably, greater than 55×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)], and, mostpreferably, greater than 60×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)] in terms ofthe oxygen permeability. By setting the oxygen permeability coefficientin this range, the burden on the eyes can be decreased and continuouswearing is facilitated when used as contact lenses.

[0065] The water content should be 15 weight % to 60 weight %,preferably, 20 weight % to 55 weight %, and, more preferably, 25 weight% to 50 weight %. When the water content is greater than 15 weight %,its action in the eyes is improved when used as a contact lens andcontinuous wearing is facilitated. When the water content is excessivelyhigh, the oxygen permeability coefficient is decreased, for which reasonthis is not desirable.

[0066] The modulus of elasticity should be 65 kPa to 2000 kPa,preferably, 100 kPa to 1400 kPa, and, most preferably, 150 kPa to 850kPa. When the modulus of elasticity is excessively low, the polymer istoo soft, so that its shape-maintaining capacity deteriorates and it isdifficult to handle, for which reason this is not desirable. When themodulus of elasticity is excessively high, the polymer is excessivelyhard and, when it is used as a contact lens, comfort on wearingdeteriorates, for which reason this is not desirable.

[0067] The monomers and polymers of this invention are particularlysuited for ophthalmic lenses such as contact lenses, intraocular lensesand artificial corneas.

[0068] We shall now describe this invention in specific terms by meansof examples. However, this invention is not limited by them.

Determination Methods

[0069] The various determinations in these examples were performed bythe methods described below.

[0070] (1) Proton Nuclear Magnetic Resonance Spectrum

[0071] Determinations were performed using Model EX270 manufactured byJEOL Ltd. Chloroform-d was used as the solvent. The chloroform peak wastaken as the internal standard (7.26 ppm).

[0072] (2) Oxygen Permeability Coefficient

[0073] The oxygen permeability coefficient of a sample in the shape of acontact lens was determined in water of 35° C. using a Seikaken-shikifilm oxygen permeability meter manufactured by RIKA SEIKI KOGYO Co.,Ltd. The film thickness of the sample was controlled according tonecessity by overlapping plurality of films.

[0074] (3) Water Content

[0075] A sample in the form of a contact lens was used. The sample wasdried for 16 hours at 40° C. in a vacuum dryer and the weight (Wd) ofthe sample was determined. Following that, it was immersed in pure waterand was impregnated with water overnight in a constant temperature tankat 40° C., after which the water on the surface was wiped off withKimwipe and its weight (Ww) was measured. The water content was found bythe following formula.

Water content (%)=100×(Ww−Wd)/Ww

[0076] (4) Modulus of Elasticity

[0077] A sample [width (smallest part), 5mm; length, 14 mm; thickness,about 0.2 mm] cut from a substance in the contact lens shape using astipulated punch mold was used, and determinations were made using ModelRTM-100 TENSILON manufactured by Orientec Corporation. The drawing ratewas set to 100 mm/min and the distance between grips was set to 5 mm.

EXAMPLE 1 Synthesis of the Compound Represented by Formula (22)

[0078]

[0079] (1) 1,3-propanediol (100 g) and potassium hydroxide (86.7 g) wereintroduced into a 500 mL three-neck distillation flask equipped with adropping funnel, a reflux condenser and a stirring blade, and themixture was stirred for about 1 hour at room temperature. Allyl bromide(159 g) was introduced through the dropping funnel and was addeddropwise while the mixture was being stirred. After the dropwiseaddition had been completed, a reaction was carried out for 3 hours at60° C. as the mixture was being stirred. Diethyl ether (250 mL) wasadded, after which the salt was removed by filtration and the solventcomponent was removed with a rotary vacuum evaporator. Because the saltagain precipitated, it was removed by filtration. Purification wasperformed by distillation under reduced pressure and 3-allyloxypropanolwas obtained as a colorless, transparent liquid.

[0080] (2) The 3-allyloxypropanol (15 g) that was synthesized in (1),triethylamine (19.6 g) and tetrahydrofuran (30 mL) were introduced intoa 300 mL three-neck distillation flask equipped with a dropping funneland a stirring blade. The three neck distillation flask was immersed inan ice bath and methacrylic acid chloride (20.2 g) was added dropwiseover a period of approximately 30 minutes as the mixture was beingstirred. After the dropwise addition was completed, stirring wascontinued for 2 hours at room temperature. The salt that precipitatedwas removed by suction and filtration. Ethyl acetate (100 mL) was addedto the filtrate which was then introduced into a separatory funnel andwas washed using a saline solution, saturated aqueous solution of sodiumhydrogen carbonate and saline solution in that order. Dehydrationtreatment was performed with anhydrous magnesium sulfate, after whichthe solvent was removed with a rotary vacuum evaporator. Purificationwas performed by distillation under reduced pressure and3-allyloxypropyl methacrylate was obtained as a colorless, transparentliquid.

[0081] (3) Chloroplatinic acid 6-hydrate was dissolved in an equalvolume of 2-propanol and was diluted to 1.93×10⁻⁵ mol/g withtetrahydrofuran. Hereafter, this solution is called the “catalystsolution.”

[0082] The 3-allyloxypropyl methacrylate (6.94 g) that was synthesizedin (2), toluene (12 g) and the catalyst solution (3.9 g) were introducedinto a 100 mL eggplant type flask equipped with a magnetic rotor. Theflask was immersed in a water bath and was cooled, and trichlorosilane(10.21 g) was added in small amounts at a time as the mixture was beingstirred. After it was confirmed that generation of heat stopped, theflask was hermetically sealed with a septum and was allowed to standovernight at room temperature. The low boiling point components wereremoved by means of a rotary vacuum evaporator, after which purificationwas performed by distillation under reduced pressure and3-(3-methacryloxypropoxy) propyl trichlorosilane was obtained as acolorless, transparent liquid. (4) Hexane (2.4 g), methanol (2.4 g), andwater (4.8 g) were introduced into a 200 mL eggplant type flask equippedwith a magnetic rotor, the flask was immersed in an ice bath and thecontents of the flask were stirred vigorously. A mixture consisting ofthe 3-(3-methacryloxypropoxy) propyl trichlorosilane(4.58 g) synthesizedin (3) and methoxytrimethyl silane (8.94 g) was added dropwise over aperiod of approximately 10 minutes. After the dropwise addition wascompleted, stirring was continued for 4 hours at room temperature. Thereaction solution was separated into two layers and the top layer wascollected with a separatory funnel. It was washed using a saturatedaqueous solution of sodium hydrogen carbonate (3 times) and water (2times) in that order. Dehydration was performed with anhydrous sodiumsulfate, after which the solvent was removed with a rotary vacuumevaporator. Purification was performed by distillation under reducedpressure and a pale yellow transparent liquid was obtained. The protonnuclear magnetic resonance spectrum of this liquid was determined andanalyzed. As a result, peaks were detected in the vicinity of 0.1 ppm(27H), in the vicinity of 0.4 ppm (2H), in the vicinity of 1.6 ppm (2H),in the vicinity of 1.9 ppm (5H), in the vicinity of 3.3 ppm (2H), in thevicinity of 3.5 ppm (2H), in the vicinity of 4.2 ppm (2H), in thevicinity of 5.5 ppm (1H) and in the vicinity of 6.1 ppm (1H). From thesefindings, it was confirmed that this was the compound represented byformula (22).

EXAMPLE 2 Synthesis of the Compound Represented by Formula (23)

[0083]

[0084] A pale yellow transparent liquid was obtained in the same way asin Example 1 except that acrylic acid chloride was used instead ofmethacrylic acid chloride. The proton nuclear magnetic resonancespectrum of this liquid was determined and analyzed. As a result, peakswere detected in the vicinity of 0.1 ppm (27H), in the vicinity of 0.4ppm (2H), in the vicinity of 1.6 ppm (2H), in the vicinity of 1.9 ppm(2H), in the vicinity of 3.3 ppm (2H). in the vicinity of 3.5 ppm (2H),in the vicinity of 4.2 ppm (2H), in the vicinity of 5.8 ppm (1H), in thevicinity of 6.2 ppm (1H) and in the vicinity of 6.4 ppm (1H). From thesefindings, it was confirmed that this was the compound represented byformula (23).

EXAMPLE 3

[0085] The Compound of formula (22) (65 parts by weight) obtained inExample 1, N,N-dimethyl acrylamide (35 parts by weight), triethyleneglycol dimethacrylate (1 part by weight), Darocure 1173 (manufactured byCIBA Specialty Chemicals Inc., 0.5 part by weight) and diethylene glycoldimethyl ether (10 parts by weight) were mixed and stirred. Ahomogeneous, transparent monomer mixture was obtained, and this monomermixture was deaerated in an argon atmosphere. It was poured into acontact lens mold made of transparent resin (poly 4-methylpentene-1) ina glove box in a nitrogen atmosphere, polymerization was performed byirradiation (1 mW/cm², 10 minutes) using an insect attraction lamp, anda contact lens-shaped sample was obtained. It was immersed 5 for 16hours at 60° C. in a large excess volume of isopropyl alcohol, afterwhich it was immersed for 24 hours in a large excess volume of purewater. Following that, it was immersed and stored in clear, pure water.The sample that was obtained was transparent and was not turbid. Theoxygen permeability coefficient of this sample was 70×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)], its water content was 30% and its modulus of elasticitywas 380 kPa. Thus, it had high oxygen permeability, high water contentand a low modulus of elasticity.

EXAMPLE 4

[0086] A contact lens-shaped sample was obtained in the same way as inExample 3 except that the compound of formula (23) (35 parts by weight)obtained in Example 2 and 3-methacryloxypropyltris (trimethylsiloxy)silane (30 parts by weight) were used instead of the compound of formula(22) (65 parts by 20 weight). The sample that was obtained wastransparent and was not turbid. The oxygen permeability coefficient ofthis sample was 75×10⁻¹¹ (cm²/sec) [mLO₂/(mL·hPa)], its water contentwas 26% and its modulus of elasticity was 280 kPa. Thus, it had highoxygen permeability, high water content and a low modulus of elasticity.

EXAMPLE 5 Synthesis of the Compound Represented by Formula (24)

[0087]

[0088] (1) Diethylene glycol (100 g) and potassium hydroxide (62.2 g)were introduced into a 500 mL three-neck distillation flask equippedwith a dropping funnel, a reflux condenser and a stirring blade, and themixture was stirred for about 1 hour at room temperature. Allyl bromide(114 g) was introduced through the dropping funnel and was addeddropwise while the mixture was being stirred. After the dropwiseaddition had been completed, a reaction was carried out for 3 hours at60° C. as the mixture was being stirred. Diethyl ether (250 mL) wasadded, after which the salt was removed by filtration and the solventcomponent was removed with a rotary vacuum evaporator. Because the saltagain precipitated, it was removed by filtration. Purification wasperformed by distillation under reduced pressure, and diethylene glycolmonoallyl ether was obtained as a colorless, transparent liquid.

[0089] (2) The diethylene glycol monoallyl ether (20 g) that wassynthesized in (1), triethylamine (20.7 g) and tetrahydrofuran (30 mL)were introduced into a 300 mL three-neck distillation flask equippedwith a dropping funnel and a stirring blade. The three-neck distillationflask was immersed in an ice bath and methacrylic acid chloride (21.4 g)was added dropwise over a period of approximately 5 minutes as themixture was being stirred. After the dropwise addition was completed,stirring was continued for 3 hours at room temperature. The salt thatprecipitated was removed by suction and filtration. Ethyl acetate (100mL) was added to the filtrate which was then introduced into aseparatory funnel and was washed using a saline solution, saturatedaqueous solution of sodium hydrogen carbonate and saline solution inthat order. Dehydration treatment was performed with anhydrous magnesiumsulfate, after which the solvent was removed with a rotary vacuumevaporator. Purification was performed by distillation under reducedpressure and 2-(2-allyloxyethoxy) ethyl methacrylate was obtained as acolorless, transparent liquid.

[0090] (3) The 2-(2-allyloxyethoxy) ethyl methacrylate (13.63 g) thatwas synthesized in (2), toluene (13 g) and the catalyst solution (6.6 g)were introduced into a 100 mL eggplant type flask equipped with amagnetic rotor. The flask was immersed in a water bath and was cooled,and trichlorosilane (17.22 g) was added in small amounts at a time asthe mixture was being stirred. After it was confirmed that generation ofheat stopped, the flask was hermetically sealed with a septum and wasallowed to stand overnight at room temperature. The low boiling pointcomponents were removed by means of a rotary vacuum evaporator, afterwhich purification was performed by distillation under reduced pressureand 3-[2-(2-methacryloxyethoxy)ethoxy] propyl trichlorosilane wasobtained as a colorless, transparent liquid.

[0091] (4) Hexane (6.0 g), methanol (6.0 g) and water (12.0 g) wereintroduced into a 200 mL eggplant type flask equipped with a magneticrotor, the flask was immersed in an ice bath and the contents of theflask were stirred vigorously. A mixture consisting of3-[2-(2-methacryloxyethoxy)ethoxy] propyl trichlorosilane (12.5 g) andmethoxytrimethyl silane (22.3 g) was added dropwise over a period ofapproximately 10 minutes. After the dropwise addition was completed,stirring was continued for 3.5 hours at room temperature. The reactionsolution was separated into two layers and the top layer was collectedwith a separatory funnel. It was washed using a saturated aqueoussolution of sodium hydrogen carbonate (3 times) and water (2 times) inthat order. Dehydration was performed with anhydrous sodium sulfate,after which the solvent was removed with a rotary vacuum evaporator.Purification was performed by distillation under reduced pressure and apale yellow transparent liquid was obtained. The proton nuclear magneticresonance spectrum of this liquid was determined and analyzed. As aresult, peaks were detected in the vicinity of 0.1 ppm (27H), in thevicinity of 0.4 ppm (2H), in the vicinity of 1.6 ppm (2H), in thevicinity of 1.9 ppm (3H), in the vicinity of 3.4 ppm (2H), in thevicinity of 3.5 to 3.8 ppm (6H), in the vicinity of 4.3 ppm (2H), in thevicinity of 5.5 ppm (1H) and in the vicinity of 6.1 ppm (1H). From thesefindings, it was confirmed that this was the compound represented byformula (24).

EXAMPLE 6 Synthesis of the Compound Represented by Formula (25)

[0092]

[0093] A pale yellow transparent liquid was obtained in the same way asin Example 1 except that acrylic acid chloride was used instead ofmethacrylic acid chloride. The proton nuclear magnetic resonancespectrum of this liquid was determined and analyzed. As a result, peakswere detected in the vicinity of 0.1 ppm (27H), in the vicinity of 0.4ppm (2H), in the vicinity of 1.6 ppm (2H), in the vicinity of 3.4 ppm(2H), in the vicinity of 3.5 to 3.8 ppm (6H), in the vicinity of 4.3 ppm(2H), in the vicinity of 5.8 ppm (1H), in the vicinity of 6.2 ppm (1H)and in the vicinity of 6.4 ppm (1H). From these findings, it wasconfirmed that this was the compound represented by formula (25).

EXAMPLE 7

[0094] The compound of formula (24) (65 parts by weight) obtained inExample 1, N,N-dimethyl acrylamide (35 parts by weight), triethyleneglycol dimethacrylate (1 part by weight), Darocure 1173 (manufactured byCIBA Specialty Chemicals Inc., 0.5 part by weight) and diethylene glycoldimethyl ether (10 parts by weight) were mixed and stirred. Ahomogeneous, transparent monomer mixture was obtained. This monomermixture was deaerated in an argon atmosphere. It was then poured into acontact lens mold made of transparent resin (poly 4-methylpentene-1) ina glove box in a nitrogen atmosphere, polymerization was performed byirradiation (1 mW/cm², 10 minutes) using an insect attraction lamp, anda contact lens-shaped sample was obtained. It was immersed for 16 hoursat 60° C. in a large excess volume of isopropyl alcohol, after which itwas immersed for 24 hours in a large excess volume of pure water.Following that, it was immersed and stored in clear, pure water. Thesample that was obtained was transparent and was not turbid. The oxygenpermeability coefficient of this sample was 69×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)], its water content was 39% and its modulus of elasticitywas 180 kPa. Thus, it had high oxygen permeability, high water contentand a low modulus of elasticity.

EXAMPLE 8

[0095] A contact lens-shaped sample was obtained in the same way as inExample 7 except that the compound of formula (25) (35 parts by weight)obtained in Example 2 and 3-methacryloxypropyltris (trimethylsiloxy)silane (30 parts by weight) were used instead of the compound of formula(24) (65 parts by weight). The sample that was obtained was transparentand was not turbid. The oxygen permeability coefficient of this samplewas 74×10⁻¹¹ (cm²/sec) [mLO₂/(mL·hPa)], its water content was 38% andits modulus of elasticity was 280 kPa. Thus, it had high oxygenpermeability, high water content and a low modulus of elasticity.

COMPARATIVE EXAMPLE 1

[0096] A contact lens-shaped sample was obtained in the same way as inExample 3 except that 3-methacryloxypropyltris (trimethylsiloxy) silane(65 parts by weight) was used instead of the compound of formula (22)(65 parts by weight). The sample that was obtained was transparent andwas not turbid. The oxygen permeability coefficient of this sample was83×10⁻¹¹ (cm²/sec) [mLO₂/(mL·hPa)], its water content was 22% and itsmodulus of elasticity was 2050 kPa. Although it had high oxygenpermeability, its water content was lower and its modulus of elasticitywas higher than in Example 3, Example 4, Example 7 and Example 8.

COMPARATIVE EXAMPLE 2

[0097]

[0098] A contact lens-shaped sample was obtained in the same way as inExample 3 except that the compound represented by formula (10) (65 partsby weight) was used instead of the compound of formula (22) (65 parts byweight). The sample that was obtained was transparent and was notturbid. The oxygen permeability coefficient of this sample was 71×10⁻¹¹(cm²/sec) [mLO₂/(mL·hPa)], its water content was 25% and its modulus ofelasticity was 830 kPa. Although it had high oxygen permeability and ahigh water content, its modulus of elasticity was higher than in Example3, Example 4, Example 7 and Example 8.

Industrial Applicability

[0099] By means of monomers of this invention, polymers and ophthalmiclenses having high oxygen permeability, high water content and a lowmodulus of elasticity are obtained.

1. A monomer that is represented by formula (1) or (2) below:X—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n)—A  (1)

wherein, X is a polymerizable group having carbon-carbon unsaturatedbonds; A is a siloxanyl group; R is H or a methyl group; m is an integerof 1 to 10; m′ is an integer of 2 to 10; and n is an integer of 2 to 10.2. The monomer of claim 1 wherein the aforementioned siloxanyl group isa substituent as represented by formula (3) below:

wherein, in formula (3), A¹ to A¹¹, respectively and independently, areh, alkyl groups of 1 to 20 carbon atoms that may be substituted or arylgroups of 6 to 20 carbon atoms that may be substituted; k is an integerof 0 to 200; and a, b and c, respectively and independently, areintegers of 0 to 20, excepting the case k=a=b=c=0.
 3. The monomer ofclaim 1 wherein X in formula (1) or (2) is one substituent selected fromsubstituents as represented by formulas (4) to (9) below:

wherein, in formulas (4) to (9), R¹ is H or a methyl group.
 4. Themonomer of claim 1 wherein, said monomer is represented by formula (1),and X is a methacryloyl group or an acryloyl group, A is one substituentselected from tris(trimethylsiloxy) silyl groups, methylbis(trimethylsiloxy) silyl groups and dimethyl (trimethylsiloxy) silylgroups, m is an integer of 1 or 2 and n is an integer of
 3. 5. Themonomer of claim 1 wherein, said monomer is represented by formula (2),and X is a methacryloyl group or an acryloyl group, R is H, A is onesubstituent selected from tris(trimethylsiloxy) silyl groups, methylbis(trimethylsiloxy) silyl groups and dimethyl (trimethylsiloxy) silylgroups, m′ is an integer of 2 or 3 and n is an integer of
 3. 6. Apolymer comprising the monomer of claim 1 as a polymerization component.7. An ophthalmic lens comprising the polymer of claim
 6. 8. A contactlens comprising the polymer of claim 6.